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arXiv:1004.2607 · Physical Review A

Accuracy of the Faddeev random phase approximation for light atoms

C. Barbieri, Dimitri Van Neck, Matthias Degroote

Published Jan 3, 2012• 8 citations
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Abstract

The accuracy of the Faddeev random phase approximation (FRPA) method is tested by evaluating total and ionization energies in the basis-set limit. A set of light atoms up to Ar is considered. Comparisons are made with the results of coupled-cluster singles and doubles (CCSD), with third-order algebraic diagrammatic construction [ADC(3)], and with the experiment. It is seen that even for two-electron systems, He and Be${}^{2+}$, the inclusion of RPA effects leads to satisfactory results, and therefore it does not overcorrelate the ground state. The FRPA becomes progressively better for larger atomic numbers, where it gives $\ensuremath{\approx}$5 mH more correlation energy, and it shifts ionization potentials by 2--10 mH with respect to the similar ADC(3) method. The ionization potentials from FRPA tend to reduce the discrepancies with the experiment.

DOI
10.1103/physreva.85.012501

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Electron correlations: I. Ground-state results in the high-density regime

R. F. Bishop, K.H. Lührmann

The coupled-cluster or $\mathrm{exp}(S)$ formalism is applied to the problem of correlations in a many-electron system. In this first work in a series of papers we concentrate on exact results and restrict ourselves to various ring approximations applicable essentially to the high-density regime. It is shown that the well-known random-phase approximation (RPA) can be formulated as a nonlinear three-dimensional integral equation for the four-point function ${S}_{2}$ which provides a measure of the two-particle---hole pair component in the true ground-state wave function. Exact analytic solutions are presented for both ${S}_{2}$ and the three-point particle-hole vertex function in the RPA, and their properties are discussed. The Tamm-Dancoff approximation to the ring summation is also formulated, and the analagous exact solutions are presented for the first time. It is demonstrated that both solutions are unique, and a comparison of the two approximations is presented in terms of the correlation energy.

Physical review. B, Condensed matter•May 15, 1978•168 citations
The accuracy of the Faddeev random phase approximation (FRPA) method is tested by evaluating total and ionization energies in the basis-set limit. A set of light atoms up to Ar is considered. Comparisons are made with the results of coupled-cluster singles and doubles (CCSD), with third-order algebraic diagrammatic construction [ADC(3)], and with the experiment. It is seen that even for two-electron systems, He and Be2+{}^{2+}2+, the inclusion of RPA effects leads to satisfactory results, and therefore it does not overcorrelate the ground state. The FRPA becomes progressively better for larger atomic numbers, where it gives \ensuremath≈\ensuremath{\approx}\ensuremath≈5 mH more correlation energy, and it shifts ionization potentials by 2--10 mH with respect to the similar ADC(3) method. The ionization potentials from FRPA tend to reduce the discrepancies with the experiment.
The spectral function of the closed-shell neon atom is computed by expanding the electron self-energy through a set of Faddeev equations. This method describes the coupling of single-particle degrees of freedom with correlated two-electron, two-hole, and electron-hole pairs. The excitation spectra are obtained using the random-phase approximation (RPA), rather than the Tamm-Dancoff framework employed in the third-order algebraic diagrammatic construction method. The difference between these two approaches is studied, as well as the interplay between ladder and ring diagrams in the self-energy. Satisfactory results are obtained for the ionization energies as well as the energy of the ground state with the Faddeev RPA scheme, which is also appropriate for the high-density electron gas.
A limitation common to all extensions of random-phase approximation including only particle-hole configurations is that they violate to some extent the energy weighted sum rules. Considering one such extension, the improved RPA (IRPA), already used to study the electronic properties of metallic clusters, we show how it can be generalized in order to eliminate this drawback. This is achieved by enlarging the configuration space, including also elementary excitations corresponding to the annihilation of a particle (hole) and the creation of another particle (hole) on the correlated ground state. The approach is tested within a solvable 3-level model.
The ground-state correlation energy calculated in the random-phase approximation (RPA) is known to be identical to that calculated using a subset of terms appearing in coupled-cluster theory with double excitations (CCD). In particular, for particle-hole (ph) RPA this equivalence requires keeping only those terms that generate time-independent ring diagrams, and for particle-particle (pp) RPA it requires keeping only those terms that generate ladder diagrams. Here I show that these identities extend to excitation energies, for which those calculated in each RPA are identical to those calculated using approximations to equation-of-motion coupled-cluster theory with double excitations (EOM-CCD). The equivalence requires three approximations to EOM-CCD: first, the ground-state CCD amplitudes are obtained from the ring-CCD or ladder-CCD equations (the same as for the correlation energy); second, the EOM eigenvalue problem is truncated to the minimal subspace, which is one particle + one hole for ph-RPA and two particles or two holes for pp-RPA; third, the similarity transformation of the Fock operator must be neglected, as it corresponds to a Brueckner-like dressing of the single-particle propagator, which is not present in the conventional RPA.
We derive a renormalized many-body perturbation theory (MBPT) starting from the random phase approximation (RPA). This RPA-renormalized perturbation theory extends the scope of single-reference MBPT methods to small-gap systems without significantly increasing the computational cost. The leading correction to RPA, termed the approximate exchange kernel (AXK), substantially improves upon RPA atomization energies and ionization potentials without affecting other properties such as barrier heights where RPA is already accurate. Thus, AXK is more balanced than second-order screened exchange [A. Grüneis et al., J. Chem. Phys. 131, 154115 (2009)], which tends to overcorrect RPA for systems with stronger static correlation. Similarly, AXK avoids the divergence of second-order Møller-Plesset (MP2) theory for small gap systems and delivers a much more consistent performance than MP2 across the periodic table at comparable cost. RPA+AXK thus is an accurate, non-empirical, and robust tool to assess and improve semi-local density functional theory for a wide range of systems previously inaccessible to first-principles electronic structure calculations.
In this second work in a series of papers the coupled-cluster or exp(S)\mathrm{exp}(S)exp(S) formalism is applied to the problem of ground-state correlations in the one-component Fermi plasma. The main approximation employed is the so-called SUB2 approximation for the two-body subsystem correlation operator S2{S}_{2}S2​ which provides a measure of the two-particle---two-hole component in the true ground-state wave function, and in which the coupling to larger subsystems is neglected. The SUB2 equations for Fermi systems are brought into tractable form by a "state-averaging" procedure which we develop by analogy with the comparable Bose equations, and which is shown by comparison with earlier exact results to be accurate in the metallic density regime at about the 1% level. Our final results for metallic densities include the completely integrated and self-consistent effects of the terms which by themselves generate (i) the random-phase approximation (RPA) and its associated exact long-range screening effects, (ii) the extra random-phase approximation exchange terms necessary to keep the RPA explicitly antisymmetric, (iii) the self-consistent particle-particle ladders (LAD) that describe two-particle scattering within the many-body medium and which describe the exact short-range behavior, (iv) a class of particle-hole ladder terms, and (v) the self-consistent hole-potential terms. Particular attention is paid to the important effects caused by the interference at intermediate separations of the long-range RPA and the short-range LAD effects. By comparison with recent and essentially exact stochastic simulations of the many-body Schr\"odinger equation, our results are seen to be accurate to about 1% for metallic densities, and hence to provide what is probably the currently best microscopic description available for this system. We show also that even in the low-density limit the SUB2 approximation provides a good "translationally-invariant-solid" description of both charged Fermi and Bose systems in this exact Wigner crystal regime.
The coupled-cluster or exp(S)\mathrm{exp}(S)exp(S) formalism is applied to the problem of correlations in a many-electron system. In this first work in a series of papers we concentrate on exact results and restrict ourselves to various ring approximations applicable essentially to the high-density regime. It is shown that the well-known random-phase approximation (RPA) can be formulated as a nonlinear three-dimensional integral equation for the four-point function S2{S}_{2}S2​ which provides a measure of the two-particle---hole pair component in the true ground-state wave function. Exact analytic solutions are presented for both S2{S}_{2}S2​ and the three-point particle-hole vertex function in the RPA, and their properties are discussed. The Tamm-Dancoff approximation to the ring summation is also formulated, and the analagous exact solutions are presented for the first time. It is demonstrated that both solutions are unique, and a comparison of the two approximations is presented in terms of the correlation energy.